Terpene derivatives



Patented Feb. I

\ Alfred L. nummelsbm-a, Wilmington, net, as-

signorjo Hercules Powder-Company, Wilmington, DeL, a corporation of Delaware so Drawing. Application my 31, 1941. Serial No. $96,222

is Glaims. '(cl. ace-92.6)

-\ 1940, and Serial No. 370,665, filed December 18,

This invention relates to a new series of terpene derivatives and more particularly to a new series of terpene derivatives resulting from the reaction of various amines with anacyclic ten-f pene having three double bonds per molecule.

Hereinafter, in this specification an acylic terpene having three double bonds permolecule will be referredto'ior convenience as an acyclic terpene.

By the method in accordance withthis' invention, a prima or secondary amine is reacted with an acycl c terpene, a'polymerized acyclic terpene, at an elevated temperature for a period designed to promote substantially complete reaction. An acid condensation catalyst will be employed under conditions to be hereinafter described. The resulting products are, in general,-

.0! the various polymeric forms of acyclic terpenes, the substantially'pure dimer will preferablybeemployed in the condensation with the i .desired'amine in accordance with this invention.

dark colored,- viscous oils and resins which-find particular use as accelerators in the vulcanization of rubber and as intermediates in the prepa ration of vulcanization accelerators.

In accordance with this invention any acyclic terpene oi the empirical iormula C1oHm,.having three double bonds per molecule, may be employed, Thus, allo-ocimene, ocin ene -or myrcene may be employed. In particular, it is preferred to employ allo-ocimene. This particular acyclic terpen'e, in addition to having three double bonds, has them in a triply conjugated position in the molecule.

As stated hereinabove, the acyclic terpenes may, it desired, be employed in p l eric form. To obtain the polymeric forms from the monomers any of the processes known in the art are contemplated.- Thus, for example, in the case of allo-ocimene, it is desired to include allo-ocl mene polymerized wlth phosphoric acid catalysts, such as, orthophosphoric acid, tetraphosphoric acid, hypophosphoric acid, metaphosphoric acid, pyrophosphoric acid, etc.; metal the use of an inert, volatile, organic solvent, such as, benzene, xylene, gasoline, ethylene dichloride,

" etc. For additional information relating to particular procedures which may be employed, see

my eopending applications'ior United States Letters Patent, Serial No. 370,664, filed December-i8,

Thus, for example; when allo-ocimene, is polymerized-in the presence of a phosphoric acid catalyst, a liquid product is formed consisting of a substantial quantity of the dimer. It has been found that the liquid product, after removal of the catalyst, --will contain from about 75% to about 95% 01 the dimer, depending upon the conditions of reaction, such as, type of phosphoric acid employed, the concentration of catalyst, the particular solvent, the reaction temperature, etc. The thiocyanate value of the product may vary from about 120 to about 240.

If desired, the product may be distilled prior to use, preferably in vacuo and over a small amount or alkali. Thereby, traces of -highe1\ polymers, catalysts and oxidation products present as impurities can be removed. The pure dimerhas the foiiowing'characteristics: I x l B. P. (4 mm.) c. 142 143 do -.0.865i 23 o I 1.508

Incarrying-out the polymerization withmeta-i halide catalysts, liquid polymers may also beobtained following the procedureoif mygi l litation for United States Letters Patent, Serial No. 370,-

. 6B4, flied December 18, 1940; however,-by employing particular metal halides and *suitably tain at least about of polymeric constitu-- controlling the conditions of reaction, solid polymers of allo-ocim'enecan result. For example, when a metal chloride, and preferably aluminum chloride, is used, generally solid polymers result. Preferably, however, to form solid polymers the reaction is carried a'ut' between about -35 .C. and about C. with the allo-oclmene dissolved in a halogenated organic solvent, such as, ethylene dichloride, etc. These solid polymers conents higher than the dimer and are further charphenylenediamine, naphthyiamine, amino biphenyl, xylidine, mesidine, cumidine, benzyiamine, phcnylethylamine, etc.; aromatic secondary amines, such as, methylaniline, ethylaniline, propylaniline, butylaniline, amylaniline, methyltoluidine, ethyltoluldinep. etc.;

butylamine, amylamine, ethylenediamine, hexamethylenediamine, dimethylamine, isopropylamine, monoethanolamine, diethanolaminej ,triethanolamine, monoisopropanolamine, etc.; aliphatic secondary amines, such as, dimethylamine, .diethylamine,

methylethylamine, etc., may be employed. Generally, 'the secondary amines react less readily than do the primary amines; hence, where sec- I ondary am nes are employed, higher 'temperatures and longer periods of reaction are required. Furthermore, aliphatic amines generally react less readily than do, the aromatic amines, hence where aliphatic amines are employed, higher temperatures and longer periods of reaction are required. J

- 'In preparing the condensation product of a monomeric or polymeric acyclic terpene with a desired amine,'the reactants are heated together,

- preferably with. agitation, in the' presence of an acid condensation catalyst at a temperature within the range of from about 150 c. to about aliphatic primary amines, such as, methylamine, ethylamine, propylamine,

250 C. for a period of from about 1 hour to about may be employed in equi-molar or other thanequi-molar proportions, although in the-reaction which ensues it is believed equi-molar proportions of the materials react. Moreover, it is preferred to employ the amine in an amount corresponding with between about a and about a 100% excess of equi-molar'proportions. The

.. acid condensation catalysts which will be employed comprise hydrochloric acid, sulfuric acid, orthophosphoric acid, t'etraphosphoric acid, fluoboric acid, hydrofluoric acid, perchloric acid, trichloracetic acid, chloraluminic acid, aromatic sulfonic acids, such as, p-toluene sulfonic acid, etc. Equivalently, the various amine salts of the aforesaid acids may be employed as catalysts, for example, aniline hydrochloride, etc. In addition, ithas been found that metal halides, such as, zinc chloride, will accomplish the desired result, but are not as desirable as the aforementioned catalysts. The amount of catalyst employed will be not greater than about 15% based on the combined weight of the, reactants. Preferably, the amount of catalyst employed will be within the range of from about 0.5% to about 10% based on the combined weight of the reactants. These ranges are based on the aforesaid acid catalysts, or as the case may be, metal halide catalysts. If an amine salt of an acid is employed as catalyst, correspondingly large quantitles will be empl yed.

Following thereaction period, the mixture will be suitably treated to remove the excess amine. For example, in the case of aniline, the mixture may be either steam or vacuo distilled to removethe excess aniline. The catalyst may be removed either prior to or after removal of the excess amine, but itis. preferably removed prior to removal of excess amine. This catalyst removal will preferably be accomplished by a combination of caustic washing and water washing.

Inert solvents may be employed-ii desired during the condensation and/or during the purification or the products. They may. comprise benzene, toluene, gasoline, cyclohexanefdecahydronaphthalene, chloroben'zene, ethylene dichloride, chloroform, etc. The use of an inert solvent will reduce the viscosity quate contact. I

y The reaction products ofthis inventionare in general dark colored viscous oils and resins. They are characterized by containing between and permit adeabout 3.0% and about10.0% of combined nitrogen.

There follow several examples which illustrate specific embodiments of the processes of this invention which, however, are not to be taken as being limiting. All parts and percentages in this specification and claims,attached are by weight unless otherwise indicated.

Example 1 One hundred'and thirty-six parts of 98% alloocimene, 120 parts of aniline and 5 parts of aniline hydrochloride were refluxed for 7 hours at 190 to 200 C. The reaction mixture was then diluted with 100 parts of benzene, and the resulti'ng solutiomwas washed with 200 parts of aqueous 10% sodium hydroxide solution. The solution was afterwards washed with water. The benzene and unreacted constituents were then removed by vacuum distillation at 10. mm. using tion gave 185 as compared with a theoretical of 229 for the condensation product of equi-molar Five: hundred parts or 98% allo-ocimene were" agitated fora period 01' 20 hours with 200 parts a final bath temperature 0! C. There remained parts of a dark colored'viscous resin which upon analysis-was found to contain 5.0% nitrogen. A Best molecular weight determinaproportions of allo-ocimeneand aniline.

Example 2 of 85% orthophosphoric acid at 25 C.- to 35 C. The reactio mixture was water washed, then washed with 600 parts or an aqueous sodium hy-' droxide solution, and again water washed. The product was distilled at 3 to 5 mm., and the fraction coming over at 0. to 0. collected.

This product was the substantially pure dimer of allo-ocimene. It had a molecular weight as determined by the Rast method 01' 270 and a thiocyanate number of 185.v

' Two hundred and seventy-two parts of the above substantially pure dimer, 150 parts 01' toluidine (commercial) and 10 parts of toluidine hydrochloride were heated at 205 C. under a reflux condenser in an atmosphere of CO3 for 12 hours. he reaction mixture was dissolved in 400 parts of xylene and the resulting solution washed with 500 parts or an aqueous 10% NaOH solution and then washed with water. The prod.-

, not was then vacuum distiliedto remove solvent and unreacted constituents, using a final bath temperature of 180 C. and a pressure of 5 mm. There remained 290 parts of a dark colored viscous resin which upon analysis was shown to contain 3.2% nitrogen. A Rast molecular weight determination gave 345 as compared with a theoreticalof 379 for the condensation product of equi-molar proportions of dimeric allo-oci v mene'and toluidine.

Example 3 To 2'72 parts of 99% allo-ocimene were added 150 parts of n-butyl amine and 15 parts of the n-butyl amine salt of sulfuric acid and the mixture heated at 210 C. in a stainless steel autoclave for a period of 18 hours. The reaction mixture was washed with aqueous 10% NaOH and finally with water. Then it was distilled at mm. to remove unreacted constituents until a bath temperature. of 150C. was reached. A viscous oil remained in the amount of 200 parts which contained 3.6% nitrogen. ular weight determination gave 170 as compared with a theoretical of 209 for a condensation product of equi-molar proportions of allo-ocimene and n-butyl amine. i

In addition to the methods of purifying the products of the invention, hereinbefore mentioned, further refinements may 'be employed, such as, treatment with a suitable activated adsorbent, such as; activated carbon, fullers earth, bauxite, silica gel, alumina, magnesium silicates, etc. The use of an inert atmosphere, such as, CO2, N2, etc., during the reaction will assist in obtaining products of improved color.

. The products of the invention are particularly useful as acceleratorsin the vulcanization'of rubber, and as intermediates inthe preparation of vulcanization-accelerators. They may also be employed as modifiers inthe preparation of aromatic amine-formaldehyde resins. Upon sulfonation with the usual sulfonating agents, the condensation products of this invention, particularly those containing aromatic groups, are converted in materials having wetting,'emulsifying and detersive properties. of the sulfonation productshave similar properties.

It will be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.

What I claim and desire to protect by Letters Patent is:

1., A reaction product of a material selected from the group'consisting ot'primary and secondary amines, and a material selected from the group consisting of acyclic terpenes, and polymerized acyclic terpenes, said acyclic terpenes having three double bonds per molecule, said reaction being carried out at a temperature within the range from about 150 0. to about 250 C., in the presence of an acid condensation catalyst.

2. A reaction product of a primary aromatic amine and allo-ocimene, said reaction being carried out at a temperature 'within the range from about 150 C. to about 250 0., in the presence of an acid condensation catalyst.

3. A reaction product of aniline and allo-ocimene, said reaction being carried out at a temerature within the range from about 150 0. to

I about 250 0., in the presence of an acid condensation catalyst.

4. A reaction product of a primary aromatic amine and polymerized 'allo-ocimene, said reaction being carried out at a temperature within the range from about 150 0. to about 250 0., in the presence of an acid condensation catalyst.

A Best molec- The alkali metal salts 5. A reaction productof a primary aromatic amine and dimeric allo-ocimene,, said reaction being carried out at a temperature within the 3 range from about C.-to about 256 0., in the presence of an acid condensation catalyst.

6. A reaction product of aniline and dimeric .-allo-ocimene, said reaction being carried out at.

a temperature within the range from about 150 -C. to about 250 0., in the presence of an acid condensation catalyst.

7. A process for making a new composition of matter which comprises reacting a materialselected from thegroup consisting of' primary and secondary amines with a'material selected from the group consisting of acyclic terpenes and polymerized acyclic terpenes, said acyclic terpenes having three double bonds per molecule, at a temperature within the range from about 150 j ature within the range of from about 150 C.

to about 250 0., in the presence of an acid condensation catalyst.

9. The process for making a new composition of matter which comprises reacting a primary aromatic amine with polymerized allo-ocimene, at a temperature within the range of from about 150 0. to about 250 0., in. the presence of an acid condensation catalyst.

10. The process for making a new composition of matter which comprises reacting a primary aromatic amine with allo-ocimene at a temperature within the range .of from about 150 C. to about 250 0., fora periodof from about 1 hour to about 24 hours, in the presence of an acid condensation catalyst.

'11. The process for making a new composition I of matter which comprises reacting a primary aromatic amine with polymerized allo-oclmene at a temperature within the range of from about 150 0. to about 250 0., for a period of from about 1 hour to about 24 hours, in the presence of an acid'condensation catalyst.

12. The process for making a new composition of matter which comprises reacting a primary aromatic amine with allo-ocimene at a temperature within the range of from about 0. to about 225 0., for a period of from about 6 hours to' about '10 hours, in the presence of an acid condensation catalyst 13. The process for making a new composition ofmatter whichcomprises reacting a primary aromatic amine with polymerized allo-ocimene at a temperature within the range of from about 175 0. to about 225 0., for a period of from about 6 hours to about 10 hours. in the presence v or an acid condensation catalyst.

14. A reaction product of an aliphatic primary amine and allo-ocimene, said reaction beingcarried out at a temperature within the range from about 150 0. to about 250 0., in the presenc of an acid'condensation catalyst. Y i 15. A reaction product of n-butyl amine and alio-ocimene, said reaction being carried out at a temperature within the range from about 150 0. to about 250 0.. in the presence of an acid condensation catalyst.

AIFRED L. Rpm-sauna. 

